Chlorofluoroalkane compositions



United States Patent 3,405,069 CHLOROFLUOROALKANE COMPQSITIONS Ralph John Gilbert Houslay and Robert Leslie McGinty,

Runcorn, England, assignors to Imperial Chemical Industries Limited, London, England, a corporation of Great Britain No Drawing. Filed Sept. 12, 1966, Ser. No. 578,485 Claims priority, application Great Britain, Sept. 16, 1965, 39,581/ 65; Nov. 24, 1965, 49,942/ 65 9 Claims. (Cl. 252182) ABSTRACT OF THE DISCLOSURE There is provided a chlorofiuoroalkane composition which is resistant to reaction between the chlorofiuoroalkane and primary and secondary polyols and amines in the composition. The improvement resides in the use of inhibitors selected from esters of salicylic acid, azoben- Zene, p amino azobenzene, pyrrole, N-methyl pyrroles, eugenol, isoeugenol, hydrazine and substituted hydrazines. The composition is useful for making polyurethane foam compositions when there is included a polyol and a polyfunctional isocyanate. The chlorofiuoroalkanes function as a blowing agent. From 0.05 to by weight of the inhibitor, based on the weight of the chlorofiuoroalkane, is included in the composition.

The present invention relates to chlorofluoroalkane compositions. More particularly it relates to compositions comprising a chlorofiuoroalkane of the methane or ethane series and compounds which inhibit reaction of the chlorofiuoroalkane with polyols and amines employed in manufacturing polyurethane foams.

Low-boiling chlorofluoroalkanes, particularly trichlorofiuoromethane, are widely used as blowing agents in producing polyurethane foams by reaction between polyols and polyfunctional isocyanates. A preferred method of producing the polyurethane foams is to incorporate the chlorofiuoroalkane blowing agent in the principal polyol component together with any cross-linking agents such as hydroxyalkylamines, glycerol or 1,3-propylene glycol, catalysts, which are usually tertiary amines, and optionally water, which acts as an additional blowing agent, and to blend the mixture with the isocyanate. The heat of reaction of the polyol (and the water when present) with the isocyanate vaporises the blowing agent and produces the desired cell structure in the polyurethane product.

Although chlorofiuoroalkanes are in general chemically inert, it has been found that they can react slowly with the polyols and also with amines, particularly with low molecular weight hydroxyalkylamines used as cross-linking agents, notably triethanolamine, causing liberation of hydrogen halide, formation of a precipitate and discolouration of the mixture. This reaction is particularly disadvantageous if it is desired to ship or to store ready for use for any significant time the chlorofluoroalkane in admixture with the polyol and possibly the reactive crosslinking agents and it has been proposed for instance, in British patent specification No. 1,009,041 to inhibit the reaction between chlorofiuoroalkanes and primary and secondary polyols by adding to compositions containing either or both the chlorofluoroalkane and the polyol certain specific olefinic compounds, for example isoprene and certain terpenes, vinyl compounds and acrylic compounds.

We have now found that the reaction of chlorofluoroalkane blowing agents with polyols and amines in polyurethane foam blowing systems can be inhibited more effectively by incorporating in compositions containing either or both the chlorofluoroalkane and the polyol a "ice small proportion of a member selected from certain specific compounds as hereinafter defined.

According to the present invention, therefore, we provide a chlorofiuoroalkane composition resistant to reaction with primary and secondary polyols and amines which comprises a chlorofiuoroalkane of the methane or ethane series and as inhibitor 0.055% (preferably 0.1- 2%) of its weight of a member of the group consisting of esters of salicylic acid, azobenzene, p-amino azobenzene, pyrrole, N-alkyl pyrroles, eugenol, isoeugenol, hydrazine and substituted hydrazines of structural formulae R (R )N.NH and R HN.NHR in which formulae R is an alkyl, carboxyalkyl, aryl, alkaryl or aralkyl radical and R is the same as R or is a hydrogen atom.

Within the scope of the invention we also provide a composition as defined in the preceding paragraph comprising additionally a polyol useful for preparing polyurethane foams by reaction with polyfunctional isocyanates in the presence of chlorofiuoroalkane blowing agents.

Furthermore we provide a composition as defined in either of the two preceding paragraphs comprising additionally triethanolamine as cross-linking agent.

A chlorofiuoroalkane composition according to the invention may contain more than one chlorofiuoroalkane of the methane or ethane series, The invention is most preferably applied to compositions comprising trichlorofiuoromethane.

Examples of suitable substituted hydrazines for use in compositions according to the invention are 1,ldimethylhydrazine, hydrazine-monoethylcarboxylate, phenyl-hydrazine, hydrazobenzene and hydrazotoluene. When hydrazine itself is employed it may be added to the compositions in the form of the readily available hydrate. It should be noted that the aromatic hydrazines, for example phenyl-hydrazine, have a very low solubility in the chlorofiuoroalkane alone, so that compositions consisting of these two components only should be well agitated to obtain uniform mixing of any solid phase before use. When the polyol component is also present the aromatic hydrazines are completely soluble in the mixture at all useful concentrations.

The polyols employed in compositions according to the invention may be any one or more of those customarily used for the production of polyurethane foams by reaction with a polyfunctional isocyanate in the presence of a chlorofiuoroalkane blowing agent. They may be of the types having ether, ester, amide or amine linkages as described for example in the said British patent specification No. 1,009,041 and in British patent specification No. 980,292. As examples of these four types of polyols may be mentioned ether condensation products of alkylene oxides with polyhydric alcohols such as sugar alcohols, trimethylolpropane and glycerol, esters of dicarboxylic acids and polyalkylene glycols, amide condensation products of polyhydric alcohols and polyfunctional isocyanates such as tolylene diisocyanate and condensation products of alkylene oxides with diamines and triamines. Polyols of the last mentioned type, for instance N,N,N,N-tetrakis(Z-hydroxypropyl)-ethylenediamine, may particularly be included in the composition along with other polyols in order to assist viscosity build-up in the early stages of the foaming process by virtue of their cross-linking properties.

The invention is further illustrated by the following examples. Ageing tests were carried out at 40 C. in glass flasks under reflux condensers, and also at 40 and at temperatures up to C. in order to accelerate the tests in tin-plated steel containers closed with tin-plated steel caps on the chlorofluoroalkane with and without stabilisers in admixture with various polyols. Stabilisers used according to the present invention were tested alongside stabilisers of the prior art, namely olefinic compounds proposed as stabilisers in the aforesaid British patent specification No. 1,009,041 and compounds which exhibit keto-enol tautomerism proposed as stabilisers in German Patent No. 1,188,277. Reaction in the mixtures was recorded by visual observation and by estimation of chloride ion liberated.

In the following tables Polyol A is the condensation product of 1 mole of sorbitol with 10 moles of propylene oxide, sold by Atlas Powder Co. under the name Atlas G2410 (Atlas is a registered trademark). Polyol B is a condensation product of triethanolamine with propylene oxide, having a hydroxyl value of about 450 mg. KOH/ g. and a viscosity of about 350 centipoises. Polyol C is a condensation product of trimethylol propane with propylene oxide, having a hydroxyl value of about 540 mg. KOH/g. and a viscosity of about 1800 centipoises. In some of the compositions mixtures of Polyol A, B or C with small amounts of commercial grade triethanolamine or N,N,N,N tetraskis(2 hydroxypropyl) ethylenediamine (available commercially under the registered trademark Quadrol) as cross-linking agents and/or small amounts of water were tested for reaction with the chlorofluoroalkane, as shown in Tables 1, 3, 5, 6, 9 and 10. All percentages are by weight. The appearance at the start of compositions containing Polyol A was very pale yellow, those containing Polyol B pale yellow, and those containing Polyol C almost colourless.

TABLE 1 Tests carried out in glass flasks at 40 C.

Compositions consisted of Polyol B (62%), triethanolamine (7%), trichlorofiuoromethane 31%, to which was added stabiliser as shown in column 1.

stabiliser, percent Duration Chloride w./w. on amount of of test, Appearance at end of ion ClrF days test liberated,

p.p.m.

None. 1 Pale yellow 390 3 .do 500 5 Yellow, solids present... 1, 630 Do. 9 Amber, solids present. 2, 210 1,1- 16 Pale yellow 280 zine, 1.0. 1,1-dimethyl-hydra- 32 -do 320 zine, 0.25. Hydrazobenzene, 1.3.. 28 Orange 880 Hydrazotoluene, 2.0.. 28 o 1,020 Pheiyl-hydrazine, 20 Yellow, trace of solids... 1, 300

0. Hydrazine-mono- 14 Pale yellow 1, 500

ethylcarboxylate 2.0 Prior-art Stabiliscrs:

Ethy1-acet0- 6 Solids present 1, 070

acetate, 1.35. Alieifiyl-acetone, 5 do 960 Ethyl-benzoyl- ..do 1,195

acetate, 0.75.

TABLE 2 Tests carried out in tin-plated steel containers at 60 C. for 7 days.

Compositions consisted of Polyol A (64%), trichlorofiuoromethane (36%), to which was added stabiliser as shown in column 1.

TABLE 3' Tests carried out in tin-plated steel containers at 60 C. for 7 days.

Compositions consisted of Polyol A (60% triethanolamine (7%), trichlorofiuoromethane (33%), to which was added stabiliser as shown in column 1.

Tests carried out in tin-plated steel containers.

Compositions consisted of Polyol B (64% trichlorofiuoromethane (36%), to which was added stabiliser as shown in column 1.

stabiliser, percent Duration Appearance Chloride w./w. on amount Temp., 01 test, at end of ion 0. days test liberated,

p.p.m.

N one 40 7 Pale yellow- 530 0.. 40 14 mixer"... 840 Do 60 7 Deep amber l, 620 1,1-dimethyl- 40 7 Pale yellow- 350 hydrazine, 0.1. 1,1-dimethyl- 40 14 .do 290 hydrazine, 0.1. 1,1-dimethyl- 00 7 Light amber 850 hydrazine, 0.5. Prior-art Stabilizers:

Limonene, 0.1. 40 7 Pale yellow- 825 Limonene, 0.5. 00 7 Amber 1, 490

TABLE 5 Tests carried out in tin-plated steel containers.

Compositions consisted of Polyol B (59%), triethanolamine (7% trichlorofiuoromethane (33 water (1%), to which was added stabiliser as shown in column 1.

Stabiliser, percent Duration Appearance Chloride w./w. on amount Temp, of test, at end ion of C ClaF C. days test liberated,

p.p.m.

None 40 14 Deep amber, 2, 350

solids present. Do 50 7 Amber, solids 1, 690

present. Do 2 .....do- 4, 400 1,1-dimethyl 40 14 Pale yellow- 220 hydrazine, 0.25.

D0 50 7 220 D0 50 7 230 1,1-dimethy1 80 2 940 hydrazine, 0.25. Hydrazobenzene, 0.25. 40 14 460 Hydrazotoluene, 0.15. 40 14 390 Prior-art stabilizers:

Isoprene, 0.3 40 14 Pale yellow- 510 Di-isobutylene, 0.25 50 7 Amber, solids 8 10 present. Do 50 7 o 850 Limonene, 0.25. 50 7 .do 1, 270 Do 50 7 do 1,070

TABLE 6 Tests carried out in tin-plated steel containers at 80 C. for 2 days.

Comparison of reactivity of unstabilised trichlorofiuoromethane (U) and trichlorofiuoromethane stabilised by addition of 0.5% w./w. of 1,1-dimethyl-hydrazine (S) with Polyols A, B and C and with these polyols in admixture with triethanolamine (TEA), Quadrol and water where shown.

Polyol type, GCLF, TEA "Quadrol" Water Appearance at end of test Chloride ion,

percent pelgcent N N 2 Y n one one e ow {Pale yellow- 200 7 None None {221%, solids present" 3, 820 m er 9 O 7 None 1 {Dark, solids present 4, 475 Amber 890 None 7 None {Reel amber- 1, 725 m er..-, 610 None 7 1 {Deep emb 2, 590 Amber 540 None None 1 {Amber. 1, 370 Pale amben- 930 7 None None {Darin solids present 4, 300 Pale yellow H 600 7 None 1 {Dark, solids present 4, 400 Pale ye ow 850 8 None 1 {Dark 3, 100 Pale yellow 850 7 None None 1 Dark, solids resent 2,460 r V 7 [Very pale yellow 400" 7 None 1 {Dark, solids present 1, 800 Very pale yellow 550 None 8 1 {Amber 1, 280 Very pale yellow 120 TABLE 7 Cm 1d Tests carried out in tin-plated steel containers at 40 C. stabilise, Appearance at end 185 e f 14 d of test liberatgd,

Compositions consisted of Polyol B (64%), trichlorofluoromethane to was added of Dark amber stabiliser calculated on the weight of the trichlorofluoro- P'ymfle 800 methane where shown in column 1. 1311881101 Chloride Stabiliser Appearancetat end rb 101% d TABLE 10 0 es 1 era e D-p- Tests carried out in tm-plated steel containers at C. None 1,320 for 14 days. I g gi g gig Compositions consisted of Polyol B (50% triethanol- Ethylgsancylaten 430 amine (20% 1,1,2, trichloro 1,2,2 trifiuoroethane gg8 (30%), to which was added 0.5% of stabiliser calcui i 300 40 lated on the wei ht of the trichlorotrifluoroethane were A g n-A o ambenzene 960 shown in column 1. Prior-art stabilizers:

Ei-isobutylene zelltow 1,3218

imonene m er cm rid Stebiliser Appoarzinticetat end 1biont d 0 es 1 era e TABLE 8 Tests carried out in tin platcd Stee C ntaine s at %\T1OIdl t gnllberhsolids present 2,

, [me T821118. ae 6 0\V 1 for 14 f f Pyrrole Dark yellow 740 Compositions consisted of Polyol B (59%), trlet l- Ethyl salicylate Deep am ber, Solids 1, e70

presen 31111 16 (7%),tr1ch10r0fluor m t (3 water Eugem, Amber 50nd, present 1, 600

to which was added 0.5% of stabiliser calculated on the weight of the trichlorofluorornethane where shown in column 1.

TABLE 9 Tests carried out in tin-plated steel containers at 40 C. for 14 days.

Compositions consisted of Polyol A (50% Quadrol (20%), 1,l,Z-trichloro-1,2,2-trifluoroethane (30%), to which was added 0.5% of stabiliser calculated on the weight of the trichlorotrifluoroethane where shown in column 1.

What we claim is:

1. A chlorofluoroalkane composition of the methane or ethane series, useful as a blowing agent in the preparation of polyurethane foams comprising as an inhibitor, from 0.055% by weight of said chlorofluoroalkane of a member selected from the group consisting of the ethyl ester of salicyclic acid, azobenzene, p-amino azobenzene, pyrrole, N-methyl pyrrole, eugenol, iso-cugenol, hydrazine, 1,1 dimethyl hydrazine, hydrazine monoethylcarboxylate, phenyl hydrazine, hydrazotoluene.

2. A composition according to claim 1, wherein the proportion of inhibitor is in the range of (ll-2% by weight of the chlorofluoroalkane.

3. A composition according to claim 1, wherein the chlorofiuoroalkane is trichlorofiuoromethane.

4. A composition according to claim 2, wherein the chlorofluoroalkane is trichlorofluoromethane.

5. A composition according to claim 1 wherein the inhibitor is selected from the group consisting of a20- benzene, ethyl salicylate, and p-amino azebenzene.

6. A composition according to claim 1, wherein the inhibitor is selected from the group consisting of pyrrole and N-methyl pyrrole.

7. A composition according to claim 1, wherein the 7 8 inhibitor is selected from the group consisting of eugenol 9. A composition according to claim 8, which further and iso-eugenol. comprises triethanolamine as a cross-linking agent.

8. A polyol composition comprising a chlorofiuoroalkane of the methane or ethane series, useful as a blowing agent in the preparation of polyurethane foams and References Cited UNITED STATES PATENTS as an inhibitor, from 0.05 %5% by Weight of said Ch'IOI' 2,848,501 8/ 1958 Lloyd 260611.5 fluoroalkane of a member selected from the group n- 2,958,711 11/1960 Skeeters 260-652.5 sisting of the ethyl ester of salicyclic acid, azobenzene, 3 0 5 11 4/1963 Kvalngs 26() 652 5 p-amino azobenzene, pyrrole, N-methyl pyrrole, eugenol, 3, 90 13 5 19 3 Long 252 138 3 X iso-eugenol, hydrazine, 1,1-dimethyl hydrazine, hydrazine I monoethylcarboxylate, phenyl hydrazine, hydrazobenzene 10 LEON ROSDOL Pr'mary Examme' and hydrozotoluene. STANLEY D. SCHWARTZ, Assistant Examiner. 

